Catalysis

Catalysis is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst[1] (/ˈkætəlɪst/), which is not consumed in the catalyzed reaction and can continue to act repeatedly. Because of this, only very small amounts of catalyst are required to alter the reaction rate in principle.[2]

In general, chemical reactions occur faster in the presence of a catalyst because the catalyst provides an alternative reaction mechanism with a lower activation energy than the non-catalyzed mechanism. In catalyzed mechanisms, the catalyst usually reacts to form a temporary intermediate, which then regenerates the original catalyst in a cyclic process.

A substance which provides a mechanism with a higher activation energy does not decrease the rate because the reaction can still occur by the non-catalyzed route.[3] An added substance which does reduce the reaction rate is not considered a catalyst[1] but a reaction inhibitor (see below).

Catalysts may be classified as either homogeneous or heterogeneous. A homogeneous catalyst is one whose molecules are dispersed in the same phase (usually gaseous or liquid) as the reactant's molecules. A heterogeneous catalyst is one whose molecules are not in the same phase as the reactant's, which are typically gases or liquids that are adsorbed onto the surface of the solid catalyst. Enzymes and other biocatalysts are often considered as a third category.

Technical perspective

In the presence of a catalyst, less free energy is required to reach the transition state, but the total free energy from reactants to products does not change.[1] A catalyst may participate in multiple chemical transformations. The effect of a catalyst may vary due to the presence of other substances known as inhibitors or poisons (which reduce the catalytic activity) or promoters (which increase the activity and also affect the temperature of the reaction).[1]

Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. A nanomaterial-based catalyst is an example of a heterogeneous catalyst. Analogous events associated with substrate binding and product dissociation apply to homogeneous catalysts.

Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by secondary processes. In heterogeneous catalysis, typical secondary processes include coking where the catalyst becomes covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve into the solution in a solid–liquid system or sublimate in a solid–gas system.

A catalyst works by providing an alternative reaction pathway to the reaction product. The rate of the reaction is increased as this alternative route has a lower activation energy than the reaction route not mediated by the catalyst. The disproportionation of hydrogen peroxide creates water and oxygen, as shown below.

2 H2O2 → 2 H2O + O2

This reaction is preferable in the sense that the reaction products are more stable than the starting material, though the uncatalysed reaction is slow. In fact, the decomposition of hydrogen peroxide is so slow that hydrogen peroxide solutions are commercially available. This reaction is strongly affected by catalysts such as manganese dioxide, or the enzyme peroxidase in organisms. Upon the addition of a small amount of manganese dioxide, the hydrogen peroxide reacts rapidly. This effect is readily seen by the effervescence of oxygen.[5] The manganese dioxide is not consumed in the reaction, and thus may be recovered unchanged, and re-used indefinitely. Accordingly, manganese dioxide catalyses this reaction.[6]

General principles

Units

Catalytic activity is usually denoted by the symbol z[7] and measured in mol/s, a unit which was called katal and defined the SI unit for catalytic activity since 1999. Catalytic activity is not a kind of reaction rate, but a property of the catalyst under certain conditions, in relation to a specific chemical reaction. Catalytic activity of one katal (Symbol 1 kat = 1 mol/s) of a catalyst means one mole of that catalyst (substance, in Mol) will catalyse 1 mole of the reactant to product in one second. A catalyst may and usually will have different catalytic activity for distinct reactions. See katal for an example.

There are further derived SI units related to catalytic activity, see the above reference for details.

Typical mechanism

Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process regenerating the catalyst. The following is a typical reaction scheme, where C represents the catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:

X + C → XC

(1)

Y + XC → XYC

(2)

XYC → CZ

(3)

CZ → C + Z

(4)

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so it does not occur in the overall reaction equation:

X + Y → Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the reaction. In practice, however, catalysts are sometimes consumed in secondary processes.

The catalyst does usually appear in the rate equation. For example, if the rate-determining step in the above reaction scheme is the first step X + C → XC, the catalyzed reaction will be second order with rate equation v = kcat[X] [C], which is proportional to the catalyst concentration [C]. However [C] remains constant during the reaction so that the catalyzed reaction is pseudo-first order:
v = kobs[X], where kobs = kcat[C].

Reaction energetics

Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical reaction X + Y to give Z. The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same.

Catalysts work by providing an (alternative) mechanism involving a different transition state and lower activation energy. Consequently, more molecular collisions have the energy needed to reach the transition state. Hence, catalysts can enable reactions that would otherwise be blocked or slowed by a kinetic barrier. The catalyst may increase reaction rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with an energy profile diagram.

In the catalyzed elementary reaction, catalysts do not change the extent of a reaction: they have no effect on the chemical equilibrium of a reaction because the rate of both the forward and the reverse reaction are both affected (see also thermodynamics). The second law of thermodynamics describes why a catalyst does not change the chemical equilibrium of a reaction. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in a reaction to move to the new equilibrium, producing energy. Production of energy is a necessary result since reactions are spontaneous only if Gibbs free energy is produced, and if there is no energy barrier, there is no need for a catalyst. Then, removing the catalyst would also result in reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be a perpetual motion machine, a contradiction to the laws of thermodynamics.[10] Thus, catalyst does not alter the equilibrium constant. (A catalyst can however change the equilibrium concentrations by reacting in a subsequent step. It is then consumed as the reaction proceeds, and thus it is also a reactant. Illustrative is the base-catalysed hydrolysis of esters, where the produced carboxylic acid immediately reacts with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.)

The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is moles per second. The productivity of a catalyst can be described by the turnover number (or TON) and the catalytic activity by the turn over frequency (TOF), which is the TON per time unit. The biochemical equivalent is the enzyme unit. For more information on the efficiency of enzymatic catalysis, see the article on enzymes.

The catalyst stabilizes the transition state more than it stabilizes the starting material. It decreases the kinetic barrier by decreasing the difference in energy between starting material and transition state. It does not change the energy difference between starting materials and products (thermodynamic barrier), or the available energy (this is provided by the environment as heat or light).

Materials

The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be made. Proton acids are probably the most widely used catalysts, especially for the many reactions involving water, including hydrolysis and its reverse. Multifunctional solids often are catalytically active, e.g. zeolites, alumina, higher-order oxides, graphitic carbon, nanoparticles, nanodots, and facets of bulk materials. Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation). Examples are nickel, such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of sulfur dioxide into sulfur trioxide by the so-called contact process. Many catalytic processes, especially those used in organic synthesis, require "late transition metals", such as palladium, platinum, gold, ruthenium, rhodium, or iridium.

Some so-called catalysts are really precatalysts. Precatalysts convert to catalysts in the reaction. For example, Wilkinson's catalyst RhCl(PPh3)3 loses one triphenylphosphine ligand before entering the true catalytic cycle. Precatalysts are easier to store but are easily activated in situ. Because of this preactivation step, many catalytic reactions involve an induction period.

Chemical species that improve catalytic activity are called co-catalysts (cocatalysts) or promotors in cooperative catalysis.

Types

Heterogeneous catalysts

The microporous molecular structure of the zeolite ZSM-5 is exploited in catalysts used in refineries

Zeolites are extruded as pellets for easy handling in catalytic reactors.

Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts are solids that act on substrates in a liquid or gaseous reaction mixture. Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen).[11] The total surface area of solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger the surface area for a given mass of particles.

A heterogeneous catalyst has active sites, which are the atoms or crystal faces where the reaction actually occurs. Depending on the mechanism, the active site may be either a planar exposed metal surface, a crystal edge with imperfect metal valence or a complicated combination of the two. Thus, not only most of the volume, but also most of the surface of a heterogeneous catalyst may be catalytically inactive. Finding out the nature of the active site requires technically challenging research. Thus, empirical research for finding out new metal combinations for catalysis continues.

For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen and hydrogen. The reacting gasesadsorb onto active sites on the iron particles. Once physically adsorbed, the reagents undergo chemisorption that results in dissociation into adsorbed atomic species, and new bonds between the resulting fragments form in part due to their close proximity. In this way the particularly strong triple bond in nitrogen is broken, which would be extremely uncommon in the gas phase due to its high activation energy. Thus, the activation energy of the overall reaction is lowered, and the rate of reaction increases. Another place where a heterogeneous catalyst is applied is in the oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid.

Heterogeneous catalysts are typically "supported," which means that the catalyst is dispersed on a second material that enhances the effectiveness or minimizes their cost. Supports prevent or reduce agglomeration and sintering of the small catalyst particles, exposing more surface area, thus catalysts have a higher specific activity (per gram) on a support. Sometimes the support is merely a surface on which the catalyst is spread to increase the surface area. More often, the support and the catalyst interact, affecting the catalytic reaction. Supports can also be used in nanoparticle synthesis by providing sites for individual molecules of catalyst to chemically bind. Supports are porous materials with a high surface area, most commonly alumina, zeolites or various kinds of activated carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.

Homogeneous catalysts

Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles involved in heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the substrates. One example of homogeneous catalysis involves the influence of H+ on the esterification of carboxylic acids, such as the formation of methyl acetate from acetic acid and methanol.[12] One high-volume process requiring a homogeneous catalyst is hydroformylation, which adds carbon monoxide to an alkene to produce an alkyl aldehyde. The aldehyde can be converted to various products such as alcohols or acids (for e.g. detergents) or polyols (for plastics such as polycarbonate or polyurethane). For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts.[13]

Organocatalysis

Whereas transition metals sometimes attract most of the attention in the study of catalysis, small organic molecules without metals can also exhibit catalytic properties, as is apparent from the fact that many enzymes lack transition metals. Typically, organic catalysts require a higher loading (amount of catalyst per unit amount of reactant, expressed in mol%amount of substance) than transition metal(-ion)-based catalysts, but these catalysts are usually commercially available in bulk, helping to reduce costs. In the early 2000s, these organocatalysts were considered "new generation" and are competitive to traditional metal(-ion)-containing catalysts. Organocatalysts are supposed to operate akin to metal-free enzymes utilizing, e.g., non-covalent interactions such as hydrogen bonding. The discipline organocatalysis is divided in the application of covalent (e.g., proline, DMAP) and non-covalent (e.g., thiourea organocatalysis) organocatalysts referring to the preferred catalyst-substratebinding and interaction, respectively.

Photocatalysts

Photocatalysis is the phenomenon where the catalyst can receive light (such as visible light), be promoted to an excited state, and then undergo intersystem crossing with the starting material, returning to ground state without being consumed. The excited state of the starting material will then undergo reactions it ordinarily could not if directly illuminated. For example, singlet oxygen is usually produced by photocatalysis. Photocatalysts are also the main ingredient in dye-sensitized solar cells.

Biocatalysts can be thought of as intermediate between homogeneous and heterogeneous catalysts, although strictly speaking soluble enzymes are homogeneous catalysts and membrane-bound enzymes are heterogeneous. Several factors affect the activity of enzymes (and other catalysts) including temperature, pH, concentration of enzyme, substrate, and products. A particularly important reagent in enzymatic reactions is water, which is the product of many bond-forming reactions and a reactant in many bond-breaking processes.

Some monoclonal antibodies whose binding target is a stable molecule which resembles the transition state of a chemical reaction can function as weak catalysts for that chemical reaction by lowering its activation energy.[15] Such catalytic antibodies are sometimes called "abzymes".

Nanocatalysts

Nanocatalysts are nanomaterials with catalytic activities. They have been extensively explored for wide range of applications. Among them, the nanocatalysts with enzyme mimicking activities are collectively called as nanozymes.[16]

Tandem catalysis

In tandem catalysis two or more different catalysts are coupled in a one-pot reaction.

Autocatalysis

In autocatalysis, the catalyst is a product of the overall reaction, in contrast to all other types of catalysis considered in this article. The simplest example of autocatalysis is a reaction of type A + B → 2 B, in one or in several steps. The overall reaction is just A → B, so that B is a product. But since B is also a reactant, it may be present in the rate equation and affect the reaction rate. As the reaction proceeds, the concentration of B increases and can accelerate the reaction as a catalyst. In effect, the reaction accelerates itself or is autocatalyzed.

A real example is the hydrolysis of an ester such as aspirin to a carboxylic acid and an alcohol. In the absence of added acid catalysts, the carboxylic acid product catalyzes the hydrolysis.

Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture.[18] In 2005, catalytic processes generated about $900 billion in products worldwide.[19] Catalysis is so pervasive that subareas are not readily classified. Some areas of particular concentration are surveyed below.

Because most bioactive compounds are chiral, many pharmaceuticals are produced by enantioselective catalysis (catalytic asymmetric synthesis).

Food processing

One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of fats using nickel catalyst to produce margarine.[20] Many other foodstuffs are prepared via biocatalysis (see below).

Environment

Catalysis impacts the environment by increasing the efficiency of industrial processes, but catalysis also plays a direct role in the environment. A notable example is the catalytic role of chlorinefree radicals in the breakdown of ozone. These radicals are formed by the action of ultravioletradiation on chlorofluorocarbons (CFCs).

Cl· + O3 → ClO· + O2

ClO· + O· → Cl· + O2

History

Generally speaking,[21] anything that increases the rate of a process is a "catalyst", a term derived from Greekκαταλύειν, meaning "to annul," or "to untie," or "to pick up." The concept of catalysis was invented by chemist Elizabeth Fulhame and described in a 1794 book, based on her novel work in oxidation-reduction experiments.[22] The first chemical reaction in organic chemistry that utilized a catalyst was studied in 1811 by Gottlieb Kirchhoff who discovered the acid-catalyzed conversion of starch to glucose. The term catalysis was later used by Jöns Jakob Berzelius in 1835[23] to describe reactions that are accelerated by substances that remain unchanged after the reaction. Fulhame, who predated Berzelius, did work with water as opposed to metals in her reduction experiments. Other 18th century chemists who worked in catalysis were Eilhard Mitscherlich[24] who referred to it as contact processes, and Johann Wolfgang Döbereiner[25][26] who spoke of contact action. He developed Döbereiner's lamp, a lighter based on hydrogen and a platinum sponge, which became a commercial success in the 1820s that lives on today. Humphry Davy discovered the use of platinum in catalysis.[27] In the 1880s, Wilhelm Ostwald at Leipzig University started a systematic investigation into reactions that were catalyzed by the presence of acids and bases, and found that chemical reactions occur at finite rates and that these rates can be used to determine the strengths of acids and bases. For this work, Ostwald was awarded the 1909 Nobel Prize in Chemistry.[28]Vladimir Ipatieff performed some of the earliest industrial scale reactions, including the discovery and commercialization of oligomerization and the development of catalysts for hydrogenation.[29]

Inhibitors, poisons, and promoters

Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and catalyst poisons if irreversible. Promoters are substances that increase the catalytic activity, even though they are not catalysts by themselves.

Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction rate.[30] However the term inhibitor is preferred since they do not work by introducing a reaction path with higher activation energy; this would not reduce the rate since the reaction would continue to occur by the non-catalyzed path. Instead they act either by deactivating catalysts, or by removing reaction intermediates such as free radicals.[30][3]

The inhibitor may modify selectivity in addition to rate. For instance, in the reduction of alkynes to alkenes, a palladium (Pd) catalyst partly "poisoned" with lead(II) acetate (Pb(CH3CO2)2) can be used.[31] Without the deactivation of the catalyst, the alkene produced would be further reduced to alkane.[32][33]

The inhibitor can produce this effect by, e.g., selectively poisoning only certain types of active sites. Another mechanism is the modification of surface geometry. For instance, in hydrogenation operations, large planes of metal surface function as sites of hydrogenolysis catalysis while sites catalyzing hydrogenation of unsaturates are smaller. Thus, a poison that covers surface randomly will tend to reduce the number of uncontaminated large planes but leave proportionally more smaller sites free, thus changing the hydrogenation vs. hydrogenolysis selectivity. Many other mechanisms are also possible.

Promoters can cover up surface to prevent production of a mat of coke, or even actively remove such material (e.g., rhenium on platinum in platforming). They can aid the dispersion of the catalytic material or bind to reagents .

Current market

The global demand for catalysts in 2010 was estimated at approximately US$29.5 billion. With the rapid recovery in the automotive and chemical industries overall, the global catalyst market is expected to experience fast growth in the coming years.[34]

^Rayner-Canham, Marelene; Rayner-Canham, Geoffrey William (2001). Women in Chemistry: Their Changing Roles from Alchemical Times to the Mid-Twentieth Century. American Chemical Society. ISBN 978-0-8412-3522-9.

Translation: I shall, therefore, to employ a well-known derivation in chemistry, call [the catalytic] bodies [i.e., substances] the catalytic force and the decomposition of [other] bodies by this force catalysis, just as we signify by the word analysis the separation of the constituents of bodies by the usual chemical affinities.

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